JP2010070720A - Epoxy resin composition and molded product - Google Patents
Epoxy resin composition and molded product Download PDFInfo
- Publication number
- JP2010070720A JP2010070720A JP2008242669A JP2008242669A JP2010070720A JP 2010070720 A JP2010070720 A JP 2010070720A JP 2008242669 A JP2008242669 A JP 2008242669A JP 2008242669 A JP2008242669 A JP 2008242669A JP 2010070720 A JP2010070720 A JP 2010070720A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- resin composition
- dihydroxybiphenyl
- curing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 152
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 152
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011256 inorganic filler Substances 0.000 claims abstract description 32
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000000465 moulding Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 53
- 230000001588 bifunctional effect Effects 0.000 claims description 16
- 150000002989 phenols Chemical class 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012776 electronic material Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 13
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 25
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 229920003986 novolac Polymers 0.000 description 15
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229940079877 pyrogallol Drugs 0.000 description 9
- -1 aromatic diamine compound Chemical class 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 230000017525 heat dissipation Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000004455 differential thermal analysis Methods 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 229910002026 crystalline silica Inorganic materials 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- XOOMNEFVDUTJPP-UHFFFAOYSA-N naphthalene-1,3-diol Chemical compound C1=CC=CC2=CC(O)=CC(O)=C21 XOOMNEFVDUTJPP-UHFFFAOYSA-N 0.000 description 4
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 4
- OENHRRVNRZBNNS-UHFFFAOYSA-N naphthalene-1,8-diol Chemical compound C1=CC(O)=C2C(O)=CC=CC2=C1 OENHRRVNRZBNNS-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 3
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 3
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 3
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 2
- RLSMYIFSFZLJQZ-UHFFFAOYSA-N 4-[4-(4-hydroxyphenoxy)phenoxy]phenol Chemical compound C1=CC(O)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(O)C=C1 RLSMYIFSFZLJQZ-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 2
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000000466 oxiranyl group Chemical group 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- XSTITJMSUGCZDH-UHFFFAOYSA-N 4-(4-hydroxy-2,6-dimethylphenyl)-3,5-dimethylphenol Chemical group CC1=CC(O)=CC(C)=C1C1=C(C)C=C(O)C=C1C XSTITJMSUGCZDH-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
- CJLPIPXJJJUBIV-UHFFFAOYSA-N 4-[3-(4-hydroxyphenoxy)phenoxy]phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC(OC=2C=CC(O)=CC=2)=C1 CJLPIPXJJJUBIV-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
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Abstract
Description
本発明は、保存安定性に優れかつ信頼性に優れた半導体封止、積層板、放熱基板等の電気・電子材料用絶縁材料として有用なエポキシ樹脂組成物及びそれを用いた成形物に関する。 The present invention relates to an epoxy resin composition useful as an insulating material for electrical and electronic materials such as semiconductor sealing, laminate, and heat dissipation substrate, which has excellent storage stability and reliability, and a molded article using the same.
従来、ダイオード、トランジスタ、集積回路等の電気、電子部品や、半導体装置等の封止方法として、例えばエポキシ樹脂やシリコン樹脂等による封止方法やガラス、金属、セラミック等を用いたハーメチックシール法が採用されていたが、近年では信頼性の向上と共に大量生産が可能で、コストメリットのあるトランスファー成形による樹脂封止が主流を占めている。 Conventionally, as a sealing method for electrical and electronic parts such as diodes, transistors, and integrated circuits, and semiconductor devices, for example, a sealing method using an epoxy resin or a silicon resin, or a hermetic sealing method using glass, metal, ceramic, or the like has been used. In recent years, resin sealing by transfer molding, which can be mass-produced with improved reliability and cost-effective, has been the mainstream in recent years.
トランスファー成形による樹脂封止に用いられる樹脂組成物においては、エポキシ樹脂と、硬化剤としてフェノール樹脂を主成分とする樹脂組成物からなる封止材料が一般的に使用されている。 In a resin composition used for resin sealing by transfer molding, a sealing material composed of an epoxy resin and a resin composition mainly composed of a phenol resin as a curing agent is generally used.
パワーデバイスなどの素子を保護する目的で使用されるエポキシ樹脂組成物は、素子が放出する多量の熱に対応するため、結晶シリカなどの無機充填材を高密度に充填している。 Epoxy resin compositions used for the purpose of protecting elements such as power devices are filled with an inorganic filler such as crystalline silica at a high density in order to cope with a large amount of heat released from the element.
パワーデバイスには、ＩＣの技術を組み込んだワンチップで構成されるものやモジュール化されたものなどがあり、封止材料に対する熱放散性、低熱膨張性の更なる向上が望まれている。 As power devices, there are ones constituted by a single chip incorporating IC technology and those made modular, and further improvements in heat dissipation and low thermal expansion for sealing materials are desired.
これらの要求に対応するべく、熱伝導率を向上するために熱伝導率の大きい結晶シリカ、窒化珪素、窒化アルミニウム、球状アルミナ粉末等の無機充填材を含有させるなどの試みがなされている（特許文献１、２）が、無機充填材の含有率を上げていくと成形時の粘度上昇とともに流動性が低下し、成形性が損なわれるという問題が生じる。従って、単に無機充填材の含有率を高める方法には限界があった。 In order to meet these demands, attempts have been made to include inorganic fillers such as crystalline silica, silicon nitride, aluminum nitride, and spherical alumina powder having high thermal conductivity in order to improve thermal conductivity (patents). As Documents 1 and 2) increase the content of the inorganic filler, there is a problem in that the fluidity decreases with increasing viscosity during molding, and the moldability is impaired. Therefore, there is a limit to the method of simply increasing the content of the inorganic filler.
上記背景から、マトリックス樹脂自体の高熱伝導率化によって組成物の熱伝導率を向上する方法も検討されている。例えば、特許文献３、特許文献４および特許文献５には、剛直なメソゲン基を有する液晶性のエポキシ樹脂およびそれを用いたエポキシ樹脂組成物が提案されている。しかし、これらのエポキシ樹脂組成物に用いる硬化剤としては、芳香族ジアミン化合物が使用されており、無機充填材の高充填率化に限界があるとともに、電気絶縁性の点でも問題があった。また、芳香族ジアミン化合物を用いた場合、硬化物の液晶性は確認できるものの、硬化物の結晶化度は低く、高熱伝導性、低熱膨張性、低吸湿性等の点で十分ではなかった。さらには液晶性発現のために、強力な磁場をかけて分子を配向させる必要があり、工業的に広く利用するためには設備的にも大きな制約があった。また、無機充填材との配合系では、マトリックス樹脂の熱伝導率に比べて無機充填材の熱伝導率が圧倒的に大きく、マトリックス樹脂自体の熱伝導率を高くしても、複合材料としての熱伝導率向上には大きく寄与しないという現実があり、十分な熱伝導率向上効果は得られていなかった。特許文献６には、硬化剤の粒径を５μｍ以下としたエポキシ樹脂組成物が開示されているが、これはポットライフの向上を主な狙いとしたものであり、熱伝導率等の物性の向上効果に関しての知見を示唆するものではない。 From the above background, a method for improving the thermal conductivity of the composition by increasing the thermal conductivity of the matrix resin itself has been studied. For example, Patent Literature 3, Patent Literature 4 and Patent Literature 5 propose a liquid crystalline epoxy resin having a rigid mesogenic group and an epoxy resin composition using the same. However, an aromatic diamine compound is used as a curing agent used in these epoxy resin compositions, and there is a limit in increasing the filling rate of the inorganic filler, and there is also a problem in terms of electrical insulation. Further, when an aromatic diamine compound is used, the liquid crystallinity of the cured product can be confirmed, but the crystallinity of the cured product is low, which is not sufficient in terms of high thermal conductivity, low thermal expansion, low hygroscopicity, and the like. Furthermore, in order to exhibit liquid crystallinity, it is necessary to orient the molecules by applying a strong magnetic field, and there are significant restrictions in terms of equipment for wide industrial use. In addition, in the compounding system with the inorganic filler, the thermal conductivity of the inorganic filler is overwhelmingly larger than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is increased, There is a reality that it does not greatly contribute to the improvement of thermal conductivity, and a sufficient effect of improving thermal conductivity has not been obtained. Patent Document 6 discloses an epoxy resin composition in which the particle size of the curing agent is 5 μm or less, which is mainly aimed at improving pot life, and has physical properties such as thermal conductivity. It does not suggest knowledge about the improvement effect.
従って、本発明の目的は、上記問題点を解消し、無機充填材と複合化させた場合の熱伝導率が高いエポキシ樹脂組成物と、それを用いた成形物を提供することである。 Accordingly, an object of the present invention is to solve the above-mentioned problems and provide an epoxy resin composition having a high thermal conductivity when combined with an inorganic filler, and a molded product using the same.
本発明者らは、特定の高結晶性化合物の微粉末を硬化剤として用いた場合、エポキシ樹脂組成物の保存安定性が大幅に向上するとともに、熱伝導率、耐熱性、低熱膨張性等の物性が特異的に向上することを見出し、本発明に到達した。 When the present inventors use a fine powder of a specific highly crystalline compound as a curing agent, the storage stability of the epoxy resin composition is greatly improved, and the thermal conductivity, heat resistance, low thermal expansion, etc. The inventors have found that the physical properties are specifically improved and have reached the present invention.
本発明は、エポキシ樹脂及び硬化剤、又はこれらと無機充填材を主成分とするエポキシ樹脂組成物において、硬化剤成分として粉末状の４，４’−ジヒドロキシビフェニルを３０ｗｔ％以上配合することを特徴とするエポキシ樹脂組成物に関する。 The present invention is characterized in that, in an epoxy resin composition mainly composed of an epoxy resin and a curing agent, or these and an inorganic filler, 30% by weight or more of powdered 4,4′-dihydroxybiphenyl is blended as a curing agent component. It relates to an epoxy resin composition.
本発明は、エポキシ樹脂及び硬化剤を含むエポキシ樹脂組成物において、硬化剤成分として平均粒径が１０μｍ以下である粉末状の４，４’−ジヒドロキシビフェニルを３０ｗｔ％以上配合することを特徴とするエポキシ樹脂組成物である。 The present invention is characterized in that, in an epoxy resin composition containing an epoxy resin and a curing agent, 30% by weight or more of powdered 4,4′-dihydroxybiphenyl having an average particle size of 10 μm or less is blended as a curing agent component. It is an epoxy resin composition.
上記エポキシ樹脂成分としては、二官能性エポキシ樹脂であることが好ましく、特に好ましくはメソゲン基を持つものである。メソゲン基を持つエポキシ樹脂としては、下記式（１）で表されるビスフェニレンユニットまたは下記式（２）で表されるナフチレンユニットを有するエポキシ樹脂が好ましく挙げられる。
好ましい二官能性のエポキシ樹脂としては、４，４’−ジヒドロキシビフェニルとジヒドロキシジフェニルメタンからなる混合物をエピクロルヒドリンによりグリシジルエーテル化して得られる結晶性のエポキシ樹脂が挙げられる。 A preferred bifunctional epoxy resin includes a crystalline epoxy resin obtained by glycidyl etherification of a mixture of 4,4'-dihydroxybiphenyl and dihydroxydiphenylmethane with epichlorohydrin.
硬化剤は、４，４’−ジヒドロキシビフェニル単独であっても、４，４’−ジヒドロキシビフェニルと４，４’−ジヒドロキシビフェニル以外の他の硬化剤からなるものであってもよい。前記他の硬化剤としては、二官能フェノール性化合物が適する。 The curing agent may be 4,4'-dihydroxybiphenyl alone or may be composed of other curing agents other than 4,4'-dihydroxybiphenyl and 4,4'-dihydroxybiphenyl. A bifunctional phenolic compound is suitable as the other curing agent.
本発明のエポキシ樹脂組成物は無機充填材を含むことができ、この場合エポキシ樹脂組成物中に無機充填材を５０〜９８ｗｔ％含有することが好ましい。また、無機充填材としては、球状のアルミナが好ましく挙げられ、この使用量は無機充填材の５０ｗｔ％以上であることがよい。 The epoxy resin composition of the present invention can contain an inorganic filler. In this case, the epoxy resin composition preferably contains 50 to 98 wt% of the inorganic filler. As the inorganic filler, spherical alumina is preferably exemplified, and the amount used is preferably 50 wt% or more of the inorganic filler.
本発明のエポキシ樹脂組成物は、電子材料用として適する。具体的には、電子材料用のプリント配線板、放熱基板、または電子部品封止材用のエポキシ樹脂組成物として適する。 The epoxy resin composition of the present invention is suitable for electronic materials. Specifically, it is suitable as a printed wiring board for electronic materials, a heat dissipation board, or an epoxy resin composition for electronic component sealing materials.
また、本発明は、上記のエポキシ樹脂組成物を、繊維状基材に含浸してなることを特徴とするプリプレグである。 Moreover, this invention is a prepreg characterized by impregnating a fibrous base material with said epoxy resin composition.
更に、本発明は、上記のエポキシ樹脂組成物を反応させて成形硬化して得られることを特徴とする硬化成形物である。 Furthermore, the present invention is a cured molded product obtained by reacting the above epoxy resin composition and molding and curing it.
上記硬化成形物は、熱伝導率が４Ｗ／ｍ・Ｋ以上であること、走査示差熱分析における融点のピークが１２０℃から２８０℃の範囲にあること、または走査示差熱分析における樹脂成分換算の吸熱量が１０Ｊ／ｇ以上であることのいずれか１以上を満足することが好ましい。 The cured molded product has a thermal conductivity of 4 W / m · K or more, a melting point peak in the scanning differential thermal analysis is in the range of 120 ° C. to 280 ° C., or a resin component conversion in the scanning differential thermal analysis. It is preferable to satisfy at least one of the endothermic amounts of 10 J / g or more.
本発明のエポキシ樹脂組成物は、熱伝導性に優れた成形物を与える。また、本発明のエポキシ樹脂組成物は、保存安定性、成形性、信頼性にも優れものとすることができ、かつ低吸水性、低熱膨張性、高耐熱性にも優れた成形物を与えることができる。そのため、本発明のエポキシ樹脂組成物は、半導体封止、積層板、放熱基板等の電気・電子材料用絶縁材料として好適に応用され、優れた高放熱性および寸法安定性が発揮される。このような特異的な効果が生ずる理由は、樹脂層の配向性が良くなり結晶性が向上するためと推察される。 The epoxy resin composition of the present invention provides a molded article having excellent thermal conductivity. In addition, the epoxy resin composition of the present invention can be excellent in storage stability, moldability and reliability, and gives a molded product excellent in low water absorption, low thermal expansion and high heat resistance. be able to. Therefore, the epoxy resin composition of the present invention is suitably applied as an insulating material for electrical / electronic materials such as semiconductor encapsulation, laminates, and heat dissipation substrates, and exhibits excellent high heat dissipation and dimensional stability. The reason why such a specific effect occurs is presumed that the orientation of the resin layer is improved and the crystallinity is improved.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のエポキシ樹脂組成物に用いる硬化剤としては、粉末状の４，４’−ジヒドロキシビフェニルを３０ｗｔ％以上含む。 As a hardening | curing agent used for the epoxy resin composition of this invention, 30 wt% or more of powdery 4,4'-dihydroxybiphenyl is included.
４，４’−ジヒドロキシビフェニルとしては微粉末のものが使用され、平均粒径が１０μｍ以下、好ましくは５μｍ以下である。４，４’−ジヒドロキシビフェニルは、高融点で高結晶性の固体であるため、粉体で配合することにより、エポキシ樹脂組成物としての保存安定性が大幅に向上する。但し、粒径が大きい場合、エポキシ樹脂組成物の加熱成形の際に未溶解部分が残存することで、硬化物が不均一となり硬化物の物性を低下させる問題があった。４，４’−ジヒドロキシビフェニル粉末の粒径は細かいものほど良いが、平均粒径を１０μｍ以下とすることで、エポキシ樹脂組成物の保存安定性を確保しつつ、硬化物の均一性が増して硬化物の物性が向上する。以下、平均粒径が１０μｍ以下、好ましくは５μｍ以下である４，４’−ジヒドロキシビフェニル粉末を、４，４’−ジヒドロキシビフェニル粉末という。 As 4,4'-dihydroxybiphenyl, fine powder is used, and the average particle size is 10 µm or less, preferably 5 µm or less. Since 4,4'-dihydroxybiphenyl is a solid having a high melting point and high crystallinity, the storage stability as an epoxy resin composition is greatly improved by blending it in powder form. However, when the particle size is large, the undissolved portion remains during the thermoforming of the epoxy resin composition, resulting in a problem that the cured product becomes non-uniform and the physical properties of the cured product are deteriorated. The finer the particle size of the 4,4′-dihydroxybiphenyl powder, the better, but by making the average particle size 10 μm or less, the uniformity of the cured product is increased while ensuring the storage stability of the epoxy resin composition. The physical properties of the cured product are improved. Hereinafter, 4,4′-dihydroxybiphenyl powder having an average particle size of 10 μm or less, preferably 5 μm or less is referred to as 4,4′-dihydroxybiphenyl powder.
４，４’−ジヒドロキシビフェニル粉末の調製方法としては、特に手法を問わないが、粉砕機による粉砕、あるいは溶媒中に溶解させ溶液とした後、貧溶媒中に滴下させて析出させる方法等を挙げることができる。粉砕は、機械式の粉砕機を用いてもよいが、より微粉化させるためにはジェットミル粉砕、湿式ボールミル粉砕を行うことが好ましい。 The method for preparing 4,4′-dihydroxybiphenyl powder is not particularly limited, and examples thereof include a method of pulverizing with a pulverizer or a method of dissolving in a solvent to form a solution and then dropping it into a poor solvent to deposit it. be able to. For the pulverization, a mechanical pulverizer may be used, but it is preferable to perform jet mill pulverization or wet ball mill pulverization in order to make the powder finer.
本発明のエポキシ樹脂組成物に用いる硬化剤としては、４，４’−ジヒドロキシビフェニル単独であっても、これと一般的にエポキシ樹脂硬化剤として知られている４，４’−ジヒドロキシビフェニル以外の他の硬化剤を必要に応じて組み合わせることができる。 The curing agent used in the epoxy resin composition of the present invention may be 4,4′-dihydroxybiphenyl alone or other than 4,4′-dihydroxybiphenyl which is generally known as an epoxy resin curing agent. Other curing agents can be combined as needed.
他の硬化剤の例を挙げれば、アミン系硬化剤、酸無水物系硬化剤、４，４’−ジヒドロキシビフェニル以外の他のフェノール系硬化剤、ポリメルカプタン系硬化剤、ポリアミノアミド系硬化剤、イソシアネート系硬化剤、ブロックイソシアネート系硬化剤等が挙げられる。これらの他の硬化剤の配合量は、配合する硬化剤の種類や得られる熱伝導性エポキシ樹脂成形体の物性を考慮して適宜設定すればよい。 Examples of other curing agents include amine curing agents, acid anhydride curing agents, phenolic curing agents other than 4,4′-dihydroxybiphenyl, polymercaptan curing agents, polyaminoamide curing agents, Isocyanate type curing agents, block isocyanate type curing agents and the like. What is necessary is just to set the compounding quantity of these other hardening | curing agents suitably considering the kind of hardening | curing agent to mix | blend, and the physical property of the heat conductive epoxy resin molded object obtained.
好ましくは４，４’−ジヒドロキシビフェニル以外の他のフェノール系硬化剤が選択される。より好ましくは、４，４’−ジヒドロキシビフェニル以外の他の二官能フェノール性化合物である。ここで、二官能フェノール性化合物は二官能フェノール性樹脂を含む意味である。 Preferably, a phenolic curing agent other than 4,4'-dihydroxybiphenyl is selected. More preferred are other bifunctional phenolic compounds other than 4,4'-dihydroxybiphenyl. Here, the bifunctional phenolic compound is meant to include a bifunctional phenolic resin.
他のフェノール系硬化剤の具体例として、ビスフェノールＡ、４，４’−ビスフェノールＦ、２，４’−ビスフェノールＦ、２，２’−ビスフェノールＦ、ビスフェノールＦの異性体混合物、４，４’−ジヒドロキシジフェニルエーテル、１，４−ビス（4−ヒドロキシフェノキシ）ベンゼン、１，３−ビス（４−ヒドロキシフェノキシ）ベンゼン、４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシジフェニルケトン、４，４’−ジヒドロキシジフェニルスルホン、２，２’−ジヒドロキシビフェニル、１０−（２，５−ジヒドロキシフェニル）−１０Ｈ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、フェノールノボラック、ビスフェノールＡノボラック、ｏ−クレゾールノボラック、ｍ−クレゾールノボラック、ｐ−クレゾールノボラック、キシレノールノボラック、ポリ−ｐ−ヒドロキシスチレン、ハイドロキノン、レゾルシン、カテコール、ｔ−ブチルカテコール、ｔ−ブチルハイドロキノン、フルオログリシノール、ピロガロール、ｔ‐ブチルピロガロール、アリル化ピロガロール、ポリアリル化ピロガロール、１，２，４−ベンゼントリオール、２，３，４−トリヒドロキシベンゾフェノン、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，４−ジヒドロキシナフタレン、２，５−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、２，８−ジヒドロキシナフタレン、上記ジヒドロキシナフタレンのアリル化物又はポリアリル化物、アリル化ビスフェノールＡ、アリル化ビスフェノールＦ、アリル化フェノールノボラック、アリル化ピロガロール等を挙げることができる。 Specific examples of other phenolic curing agents include bisphenol A, 4,4′-bisphenol F, 2,4′-bisphenol F, 2,2′-bisphenol F, isomer mixtures of bisphenol F, 4,4′- Dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) benzene, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4 '-Dihydroxydiphenylsulfone, 2,2'-dihydroxybiphenyl, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-crezo All novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated Pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, , 6-Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihi Roxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allyl Pyrogallol and the like.
上記他の二官能フェノール性化合物の中で、特に好ましいものは、具体的にはヒドロキノン、４，４’−ジヒドロキシジフェニルメタン、ビスフェノールＦ（異性体混合物）、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシベンゾフェノン、１，４−ビス（４−ヒドロキシフェノキシ）ベンゼン、４，４’−ジヒドロキシジフェニルスルフィド、１，５−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレンを例示することができる。これら他の二官能性フェノール化合物の使用量は、硬化剤成分中７０ｗｔ％以下であるが、好ましくは５０ｗｔ％以下である。また、これら他の二官能性フェノール化合物を４，４’−ジヒドロキシビフェニル粉末と併用することにより成形性、低熱膨張性等の性状のいくつかを改良することができ、このような場合は硬化剤成分中３０〜６０ｗｔ％を使用することがよい。 Among the above-mentioned other bifunctional phenolic compounds, particularly preferred are hydroquinone, 4,4′-dihydroxydiphenylmethane, bisphenol F (isomer mixture), 4,4′-dihydroxydiphenyl ether, 4,4 Examples include '-dihydroxybenzophenone, 1,4-bis (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. be able to. The amount of these other difunctional phenol compounds used is 70 wt% or less in the curing agent component, but preferably 50 wt% or less. Further, by using these other bifunctional phenol compounds in combination with 4,4′-dihydroxybiphenyl powder, some properties such as moldability and low thermal expansion can be improved. It is good to use 30-60 wt% in a component.
本発明のエポキシ樹脂組成物は、４，４’−ジヒドロキシビフェニル粉末の配合割合が硬化剤成分中３０ｗｔ％以上であれば、上記したように他の硬化剤を含んでいても良いが、硬化剤中に３官能以上の多官能性の化合物の含有率が高くなると、硬化後の分子の並びの規則性が低下し、高熱伝導性、低熱膨張性、低吸湿性等の効果が低下するため、４，４’−ジヒドロキシビフェニル粉末と他の二官能性のフェノール性化合物の合計量が好ましくは８０ｗｔ％以上、より好ましくは９０ｗｔ％以上とすることがよい。 The epoxy resin composition of the present invention may contain other curing agents as described above as long as the blending ratio of the 4,4′-dihydroxybiphenyl powder is 30 wt% or more in the curing agent component. If the content of the trifunctional or higher polyfunctional compound is increased, the regularity of the alignment of molecules after curing decreases, and the effects such as high thermal conductivity, low thermal expansion, and low hygroscopicity decrease. The total amount of 4,4′-dihydroxybiphenyl powder and other difunctional phenolic compound is preferably 80 wt% or more, more preferably 90 wt% or more.
本発明のエポキシ樹脂組成物では、エポキシ樹脂と硬化剤の配合比率は、エポキシ基と硬化剤中の官能基が当量比で０．８〜１．５の範囲である。この範囲外では硬化後も未反応のエポキシ基、又は硬化剤中の官能基が残留し、電気絶縁材料としての信頼性が低下するため好ましくない。 In the epoxy resin composition of this invention, the compounding ratio of an epoxy resin and a hardening | curing agent is the range of 0.8-1.5 by the equivalent ratio of the functional group in an epoxy group and a hardening | curing agent. Outside this range, an unreacted epoxy group or a functional group in the curing agent remains even after curing, which is not preferable because reliability as an electrical insulating material is lowered.
本発明のエポキシ樹脂組成物に用いるエポキシ樹脂は、分子中にエポキシ基を２つ以上有するものであればよい。例を挙げれば、ビスフェノールＡ、４，４’−ジヒドロキシジフェニルメタン、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルフィド、フルオレンビスフェノール、４，４’−ビフェノール、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシビフェニル、２，２’−ビフェノール、レゾルシン、カテコール、ｔ−ブチルカテコール、ｔ−ブチルハイドロキノン、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、1,5‐ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，４−ジヒドロキシナフタレン、２，５−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、２，８−ジヒドロキシナフタレン、上記ジヒドロキシナフタレンのアリル化物又はポリアリル化物、アリル化ビスフェノールＡ、アリル化ビスフェノールＦ、アリル化フェノールノボラック等の２価のフェノール類、あるいは、フェノールノボラック、ビスフェノールＡノボラック、ｏ−クレゾールノボラック、ｍ−クレゾールノボラック、ｐ−クレゾールノボラック、キシレノールノボラック、ポリ−ｐ−ヒドロキシスチレン、トリス−（４−ヒドロキシフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、フルオログリシノール、ピロガロール、ｔ−ブチルピロガロール、アリル化ピロガロール、ポリアリル化ピロガロール、１，２，４−ベンゼントリオール、２，３，４−トリヒドロキシベンゾフェノン、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、ジシクロペンタジエン系樹脂等の３価以上のフェノール類、または、テトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類から誘導されるグリシジルエーテル化物等がある。これらのエポキシ樹脂は、１種または２種以上を混合して用いることができる。 The epoxy resin used for the epoxy resin composition of this invention should just have two or more epoxy groups in a molecule | numerator. Examples include bisphenol A, 4,4′-dihydroxydiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylsulfone, 4,4 ′. -Dihydroxydiphenyl sulfide, fluorene bisphenol, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2'-biphenol, resorcin, catechol, t-butyl Catechol, t-butylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, , 3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated product or polyallylated product of the above-mentioned dihydroxynaphthalene Divalent phenols such as allylated bisphenol A, allylated bisphenol F and allylated phenol novolak, or phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, Poly-p-hydroxystyrene, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fluoroglycino Pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylized pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, etc. There are glycidyl ethers derived from trivalent or higher phenols or halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or in combination of two or more.
本発明に用いるエポキシ樹脂として特に好ましいのは、二官能性のエポキシ樹脂であるが、特に好ましいものは、分子中にメソゲン基を１つ以上持つエポキシ樹脂である。 Particularly preferred as the epoxy resin used in the present invention is a bifunctional epoxy resin, and particularly preferred is an epoxy resin having one or more mesogenic groups in the molecule.
ここで、メソゲン基とは、液晶性を発現するために必要な剛直構造を有する二価の有機基であり、液晶物質にその例を見ることができる。液晶物質としては、例えば、Liquid Crystals in Tabellen II， D． Demes etal Eds.， VEB Deutscher Verlag fur grundstoffindustrie， Leipzig（1984）を参考とすることができる。また、メソゲン基を持つエポキシ樹脂は、上記特許文献３〜５等により公知である。 Here, the mesogenic group is a divalent organic group having a rigid structure necessary for exhibiting liquid crystallinity, and examples thereof can be found in liquid crystal substances. As the liquid crystal substance, for example, Liquid Crystals in Tabellen II, D.I. Reference can be made to Demes etal Eds., VEB Deutscher Verlag fur grundstoffindustrie, Leipzig (1984). Moreover, the epoxy resin which has a mesogenic group is well-known by the said patent documents 3-5.
メソゲン基を持つエポキシ樹脂としては、上記式（１）で表されるビスフェニレンユニットを持つエポキシ樹脂、および上記式（２）で表されるナフチレンユニットを持つエポキシ樹脂を好ましく挙げることができる。 Preferred examples of the epoxy resin having a mesogenic group include an epoxy resin having a bisphenylene unit represented by the above formula (1) and an epoxy resin having a naphthylene unit represented by the above formula (2).
上記式（１）において、Ｙは、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子、炭素数１〜８の炭化水素基、炭素数１〜８のアルコキシ基を示すが、一分子中にＹが２つ以上ある場合、それらが同一であっても良いし、異なっていても良い。それらの置換位置としては、一分子中のそれぞれのベンゼン環において、同じ位置でも良いし、異なった位置に置換していてもよく、式（１）のメソゲン基は、必ずしも対称性のある構造である必要はない。また、Ｘは単結合、−ＣＨ＝ＣＨ−基、−ＣＨ＝Ｃ（Ｍｅ）−基、−ＣＨ＝Ｃ（ＣＮ）−基、−Ｃ≡Ｃ−基、−ＣＨ＝Ｎ−基、−ＣＨ＝Ｎ（→Ｏ）−基、−ＣＨ＝ＣＨ−ＣＯ−基、−Ｎ＝Ｎ−基、−Ｎ＝Ｎ（→Ｏ）−基、−ＣＯＯ−基、−ＣＯＮＨ−基または−ＣＯ−基を示す。ここで、一分子中に２つ以上のＸを有し、かつＸが非対称性の基である場合、その置換位置は全てが同じ向きでも良いし異なっていても良い。また、ｎは１〜３の数であり、ｍは０〜４の数である。Ｍｅはメチル基である。 In the above formula (1), Y represents a halogen atom such as F, Cl, or Br, a hydrocarbon group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and two Y atoms per molecule. When there are the above, they may be the same or different. These substitution positions may be the same or different at each benzene ring in one molecule, and the mesogenic group of the formula (1) is not necessarily a symmetrical structure. There is no need. X is a single bond, —CH═CH— group, —CH═C (Me) — group, —CH═C (CN) — group, —C≡C— group, —CH═N— group, —CH ═N (→ O) — group, —CH═CH—CO— group, —N═N— group, —N═N (→ O) — group, —COO— group, —CONH— group or —CO— group. Indicates. Here, when two or more Xs are contained in one molecule and X is an asymmetric group, all of the substitution positions may be the same or different. N is a number from 1 to 3, and m is a number from 0 to 4. Me is a methyl group.
また、上記式（２）で表されるナフチレンユニットとしては、１，４−ナフチレン基、１，５−ナフチレン基、２，６−ナフチレン基、２，７−ナフチレン基が好ましい。 Moreover, as a naphthylene unit represented by the said Formula (2), a 1, 4- naphthylene group, a 1, 5- naphthylene group, a 2, 6- naphthylene group, and a 2, 7- naphthylene group are preferable.
メソゲン基を持つエポキシ樹脂において、エポキシ基は、上記メソゲン基に直接、オキシラン基、グリシジル基、あるいはグリシジルエーテル基が結合したものでも良いし、柔軟性のあるスペーサー基としての炭素数２〜３０程度のアルカン鎖あるいはオキシアルカン鎖を介して、オキシラン基、グリシジル基、あるいはグリシジルエーテル基が結合したものであってもよい。 In the epoxy resin having a mesogen group, the epoxy group may be one in which an oxirane group, a glycidyl group, or a glycidyl ether group is directly bonded to the mesogen group, or about 2 to 30 carbon atoms as a flexible spacer group. An oxirane group, a glycidyl group, or a glycidyl ether group may be bonded via an alkane chain or an oxyalkane chain.
中でも、好ましいメソゲン基を持つエポキシ樹脂は、下記式（３）において、Ｘが単結合、−ＣＨ＝ＣＨ−基、−ＣＯＯ−基、−ＣＯＮＨ−基または−ＣＯ−基で、Ｙが水素原子またはメチル基であり、ｐが０から６の数であるエポキシ樹脂、または下記式（４）において、Ｘが単結合、−ＣＨ＝ＣＨ−基、−ＣＯＯ−基、−ＣＯＮＨ−基または−ＣＯ−基で、Ｙが水素原子またはメチル基であり、ｑが１から１８の数であるエポキシ樹脂である。 Among them, an epoxy resin having a preferred mesogenic group is represented by the following formula (3), wherein X is a single bond, —CH═CH— group, —COO— group, —CONH— group or —CO— group, and Y is a hydrogen atom. Or an epoxy resin which is a methyl group and p is a number from 0 to 6, or in the following formula (4), X is a single bond, —CH═CH— group, —COO— group, —CONH— group or —CO -An epoxy resin in which Y is a hydrogen atom or a methyl group and q is a number from 1 to 18.
メソゲン基を持つエポキシ樹脂の製法は、特に限定されるものではないが、メソゲン基を持つジヒドロキシ体とエピクロルヒドリンを反応させることにより製造することができる。この反応は、通常のエポキシ化反応と同様に行うことができる。 Although the manufacturing method of the epoxy resin which has a mesogen group is not specifically limited, It can manufacture by making the dihydroxy body which has a mesogen group, and epichlorohydrin react. This reaction can be performed in the same manner as a normal epoxidation reaction.
例えば、メソゲン基を持つジヒドロキシ体を過剰のエピクロルヒドリンに溶解した後、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物の存在下に、５０〜１５０℃、好ましくは、６０〜１００℃の範囲で１〜１０時間反応させる方法が挙げられる。この際の、アルカリ金属水酸化物の使用量は、ジヒドロキシ体中の水酸基１モルに対して、０．８〜１．２モル、好ましくは、０．９〜１．０モルの範囲である。エピクロルヒドリンは、ジヒドロキシ体中の水酸基に対して過剰量が用いられ、通常は、ジヒドロキシ体中の水酸基１モルに対して、１．５から１５モルである。反応終了後、過剰のエピクロルヒドリンを留去し、残留物をトルエン、メチルイソブチルケトン等の溶剤に溶解し、濾過し、水洗して無機塩を除去し、次いで溶剤を留去することにより目的のエポキシ樹脂を得ることができる。なお、本発明のエポキシ樹脂組成物に用いるエポキシ樹脂としてメソゲン基を持たないエポキシ樹脂を使用する場合、そのエポキシ樹脂はメソゲン基を持たないジヒドロキシ体を使用する他は、上記と同様にして製造することができる。 For example, a dihydroxy compound having a mesogenic group is dissolved in excess epichlorohydrin and then in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, preferably in the range of 50 to 150 ° C., preferably 60 to 100 ° C. And reacting for 1 to 10 hours. In this case, the amount of the alkali metal hydroxide used is in the range of 0.8 to 1.2 mol, preferably 0.9 to 1.0 mol, relative to 1 mol of the hydroxyl group in the dihydroxy body. Epichlorohydrin is used in an excess amount with respect to the hydroxyl group in the dihydroxy body, and is usually 1.5 to 15 moles relative to 1 mole of the hydroxyl group in the dihydroxy body. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy is removed by distilling off the solvent. A resin can be obtained. In addition, when using the epoxy resin which does not have a mesogen group as an epoxy resin used for the epoxy resin composition of this invention, the epoxy resin is manufactured similarly to the above except using a dihydroxy body which does not have a mesogen group. be able to.
本発明のエポキシ樹脂組成物に用いるエポキシ樹脂は、メソゲン基を持つジヒドロキシ体とメソゲン基を持たない他のフェノール性化合物と混合させたものを用いて合成することもできる。この場合のメソゲン基を持つジヒドロキシ体の混合比率は５０ｗｔ％以上であることがよい。この場合の他のフェノール性化合物には特に制約はなく、一分子中に水酸基を２個以上有するものの中から選択される。 The epoxy resin used for the epoxy resin composition of the present invention can also be synthesized using a mixture of a dihydroxy compound having a mesogenic group and another phenolic compound having no mesogenic group. In this case, the mixing ratio of the dihydroxy compound having a mesogenic group is preferably 50 wt% or more. Other phenolic compounds in this case are not particularly limited, and are selected from those having two or more hydroxyl groups in one molecule.
本発明のエポキシ樹脂組成物に用いるエポキシ樹脂、特にメソゲン基を持つエポキシ樹脂は、通常、常温で結晶性を有するものがよい。好ましい融点の範囲は５０℃〜２５０℃であり、より好ましくは、６０℃〜１５０℃の範囲である。これより低いとブロッキング等が起こりやすくなり固体としての取扱い性に劣り、これより高いと硬化剤等との相溶性、溶剤への溶解性等が低下する。 The epoxy resin used in the epoxy resin composition of the present invention, particularly an epoxy resin having a mesogenic group, usually has crystallinity at room temperature. The range of preferable melting | fusing point is 50 to 250 degreeC, More preferably, it is the range of 60 to 150 degreeC. If it is lower than this, blocking and the like are likely to occur, resulting in poor handling as a solid, and if it is higher than this, compatibility with a curing agent or the like, solubility in a solvent, and the like are reduced.
本発明のエポキシ樹脂組成物に用いるエポキシ樹脂、特にメソゲン基を持つエポキシ樹脂の純度、特に加水分解性塩素量は、適用する電子部品の信頼性向上の観点より少ない方がよい。特に限定するものではないが、好ましくは１０００ｐｐｍ以下、さらに好ましくは５００ｐｐｍ以下である。なお、本発明でいう加水分解性塩素とは、以下の方法により測定された値をいう。すなわち、試料０．５ｇをジオキサン３０ｍｌに溶解後、１Ｎ−ＫＯＨ、１０ｍｌを加え３０分間煮沸還流した後、室温まで冷却し、さらに８０％アセトン水１００ｍｌを加え、０．００２Ｎ−ＡｇＮＯ3水溶液で電位差滴定を行い得られる値である。 The purity of the epoxy resin used in the epoxy resin composition of the present invention, particularly the epoxy resin having a mesogenic group, particularly the amount of hydrolyzable chlorine, is better from the viewpoint of improving the reliability of the applied electronic component. Although it does not specifically limit, Preferably it is 1000 ppm or less, More preferably, it is 500 ppm or less. In addition, the hydrolyzable chlorine as used in the field of this invention means the value measured by the following method. That is, the potential difference the sample 0.5g were dissolved in dioxane 30 ml, 1N-KOH, after the added boiled under reflux for 30 minutes 10 ml, cooled to room temperature, 80% aqueous acetone 100ml was added, with 0.002 N-AgNO 3 aqueous solution This is a value obtained by titration.
本発明のエポキシ樹脂組成物に用いるエポキシ樹脂のエポキシ当量は、通常１５０から６００の範囲であるが、無機フィラーの高充填率化および流動性向上の観点から低粘度性のものが好ましく、エポキシ当量が１６０から４００の範囲のものが好ましい。エポキシ樹脂を複数使用する場合のエポキシ当量は、合計のエポキシ樹脂（ｇ）/合計のエポキシ基（モル）で計算される。 The epoxy equivalent of the epoxy resin used in the epoxy resin composition of the present invention is usually in the range of 150 to 600, but from the viewpoint of increasing the filling rate of the inorganic filler and improving the fluidity, those having low viscosity are preferred, and the epoxy equivalent Is preferably in the range of 160 to 400. The epoxy equivalent in the case of using a plurality of epoxy resins is calculated by (total epoxy resin (g) / total epoxy groups (mol)).
本発明のエポキシ樹脂組成物に用いるメソゲン基を持つエポキシ樹脂の配合割合は、全エポキシ樹脂の５０ｗｔ％以上が好ましく、より好ましくは８０ｗｔ％以上である。さらには、二官能性エポキシ樹脂の合計量が９０ｗｔ％以上、好ましくは９５ｗｔ％以上であることが望ましい。これより少ないと硬化物とした際の熱伝導率等の物性向上効果が小さい。これは、メソゲン基を持つエポキシ樹脂の含有率が高く、かつ二官能性エポキシ樹脂の含有率が高いものほど、成形物としての結晶化度が高くなるためである。また、メソゲン基を有しないエポキシ樹脂と併用することにより成形性、低熱膨張性等の性状のいくつかを改良することができ、このような場合はメソゲン基を１つ以上持つエポキシ樹脂はエポキシ樹脂の２０〜５０ｗｔ％を使用することがよい。 The blending ratio of the epoxy resin having a mesogenic group used in the epoxy resin composition of the present invention is preferably 50 wt% or more, more preferably 80 wt% or more of the total epoxy resin. Furthermore, it is desirable that the total amount of the bifunctional epoxy resin is 90 wt% or more, preferably 95 wt% or more. If it is less than this, the effect of improving physical properties such as thermal conductivity when cured is small. This is because the higher the content of the epoxy resin having a mesogenic group and the higher the content of the bifunctional epoxy resin, the higher the crystallinity as a molded product. In addition, some properties such as moldability and low thermal expansion can be improved by using together with an epoxy resin having no mesogenic group. In such a case, an epoxy resin having one or more mesogenic groups is an epoxy resin. It is preferable to use 20 to 50 wt% of the above.
メソゲン基を持つエポキシ樹脂以外のエポキシ樹脂としては、下記一般式（５）で表されるビスフェノール系エポキシ樹脂が好ましい。
これらのエポキシ樹脂は、例えば、ヒドロキノン、４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルスルフィドを原料として、通常のエポキシ化反応を行うことで合成することができる。これらのエポキシ樹脂は、原料段階でメソゲン基を持つジヒドロキシ化合物と混合させたものを用いて合成してもよい。中でも、４，４’−ジヒドロキシビフェニルと４，４’−ジヒドロキシジフェニルメタンからなる混合物がエピクロルヒドリンによりグリシジルエーテル化された結晶性のエポキシ樹脂が好ましい。この場合、４，４’−ジヒドロキシビフェニルを５０〜８０wt％、４，４’−ジヒドロキシジフェニルメタンを２０〜５０wt％使用することがよい。 These epoxy resins can be synthesized by performing a normal epoxidation reaction using, for example, hydroquinone, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, and 4,4′-dihydroxydiphenyl sulfide as raw materials. Can do. You may synthesize | combine these epoxy resins using what was mixed with the dihydroxy compound which has a mesogen group in a raw material stage. Among these, a crystalline epoxy resin obtained by glycidyl etherification of a mixture of 4,4'-dihydroxybiphenyl and 4,4'-dihydroxydiphenylmethane with epichlorohydrin is preferable. In this case, it is preferable to use 50 to 80 wt% of 4,4'-dihydroxybiphenyl and 20 to 50 wt% of 4,4'-dihydroxydiphenylmethane.
本発明のエポキシ樹脂組成物には、無機充填材が配合されることが好ましい。この場合の無機充填材の添加量は、通常、エポキシ樹脂組成物に対して５０〜９８ｗｔ％であるが、好ましくは８０〜９６ｗｔ％、さらに好ましくは８６〜９６ｗｔ％である。これより少ないと高熱伝導性、低熱膨張性、高耐熱性等の効果が十分に発揮されない。これらの効果は、無機充填材の添加量が多いほど向上するが、その体積分率に応じて向上するものではなく、特定の添加量以上となった時点から飛躍的に向上する。これらの物性は、高分子状態での高次構造が制御された効果によるものであり、この高次構造が主に無機充填材表面で達成されることから、特定量の無機充填材を必要とするものであると考えられる。一方、無機充填材の添加量がこれより多いと粘度が高くなり、成形性が悪化する。 The epoxy resin composition of the present invention preferably contains an inorganic filler. In this case, the amount of the inorganic filler added is usually 50 to 98 wt% with respect to the epoxy resin composition, preferably 80 to 96 wt%, and more preferably 86 to 96 wt%. If it is less than this, effects such as high thermal conductivity, low thermal expansion, and high heat resistance will not be sufficiently exhibited. These effects are improved as the added amount of the inorganic filler is increased, but are not improved in accordance with the volume fraction, and are drastically improved from the point when the added amount exceeds the specific amount. These physical properties are due to the effect of controlling the higher order structure in the polymer state, and since this higher order structure is achieved mainly on the surface of the inorganic filler, a specific amount of inorganic filler is required. It is thought to be. On the other hand, when the added amount of the inorganic filler is larger than this, the viscosity is increased and the moldability is deteriorated.
無機充填材は球状のものが好ましく、断面が楕円上であるものも含めて球状であれば特に限定されるものではないが、流動性改善の観点からは、極力真球状に近いものであることが特に好ましい。これにより、面心立方構造や六方稠密構造等の最密充填構造をとり易く、充分な充填量を得ることができる。球形でない場合、充填量が増えると充填材同士の摩擦が増え、上記の上限に達する前に流動性が極端に低下して粘度が高くなり、成形性が悪化する。 The inorganic filler is preferably spherical and is not particularly limited as long as it has a spherical shape including those having a cross section on an ellipse, but from the viewpoint of improving fluidity, it should be as close to a true sphere as possible. Is particularly preferred. Thereby, it is easy to take a close-packed structure such as a face-centered cubic structure or a hexagonal close-packed structure, and a sufficient filling amount can be obtained. When the amount is not spherical, the friction between the fillers increases as the filling amount increases, and before reaching the above upper limit, the fluidity is extremely lowered to increase the viscosity and the moldability is deteriorated.
熱伝導率向上の観点からは、無機充填材の５０ｗｔ％以上、好ましくは８０ｗｔ％以上を、熱伝導率が５Ｗ／ｍ・Ｋ以上のものとすることがよい。かかる無機充填材としては、アルミナ、窒化アルミニウム、結晶シリカ等が好適である。これらの中でも、球状アルミナが優れる。その他、必要に応じて形状に関係なく無定形無機充填材、例えば溶融シリカ、結晶シリカなどを併用しても良い。 From the viewpoint of improving thermal conductivity, it is preferable that 50 wt% or more, preferably 80 wt% or more of the inorganic filler has a thermal conductivity of 5 W / m · K or more. As such an inorganic filler, alumina, aluminum nitride, crystalline silica and the like are suitable. Among these, spherical alumina is excellent. In addition, an amorphous inorganic filler such as fused silica or crystalline silica may be used in combination, if necessary, regardless of the shape.
また、無機充填材の平均粒径は１０μｍ以下であることが好ましい。平均粒径がこれより大きいとエポキシ樹脂組成物の流動性が損なわれ、また強度も低下する。 Moreover, it is preferable that the average particle diameter of an inorganic filler is 10 micrometers or less. If the average particle size is larger than this, the fluidity of the epoxy resin composition is impaired, and the strength is also lowered.
本発明のエポキシ樹脂組成物には、従来より公知の硬化促進剤を用いることができる。例を挙げれば、アミン類、イミダゾール類、有機ホスフィン類、ルイス酸等があり、具体的には、１，８−ジアザビシクロ（５，４，０）ウンデセン−７、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノールなどの三級アミン、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−へプタデシルイミダゾールなどのイミダゾール類、トリブチルホスフィン、メチルジフェニルホスフイン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィンなどの有機ホスフィン類、テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・エチルトリフェニルボレート、テトラブチルホスホニウム・テトラブチルボレートなどのテトラ置換ホスホニウム・テトラ置換ボレート、２−エチル−４−メチルイミダゾール・テトラフェニルポレート、Ｎ−メチルモルホリン・テトラフェニルポレートなどのテトラフェニルボロン塩などがある。 A conventionally well-known hardening accelerator can be used for the epoxy resin composition of this invention. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenyl Rate, tetra-substituted phosphonium tetra-substituted borate such as tetrabutylphosphonium-tetrabutyl borate, 2-ethyl-4-methylimidazole · tetraphenyl port rate, and the like tetraphenyl boron salts such as N- methylmorpholine-tetraphenyl port rate.
上記硬化促進剤の添加量は、エポキシ樹脂と硬化剤の合計に対して、０．１〜１０．０ｗｔ％が好ましい。０．１ｗｔ％未満ではゲル化時間が遅くなって加熱反応時の剛性低下による作業性の低下をもたらし、逆に１０．０ｗｔ％を超えると成形途中で反応が進んでしまい、未充填が発生し易くなる。 As for the addition amount of the said hardening accelerator, 0.1-10.0 wt% is preferable with respect to the sum total of an epoxy resin and a hardening | curing agent. If it is less than 0.1 wt%, the gelation time will be delayed, resulting in a decrease in workability due to a decrease in rigidity during the heating reaction. Conversely, if it exceeds 10.0 wt%, the reaction will progress during the molding and unfilling will occur. It becomes easy.
本発明のエポキシ樹脂組成物においては、上記成分の他に、離型剤、カップリング剤、熱可塑性のオリゴマー類、その他の一般的にエポキシ樹脂組成物に使用可能なものを適宜配合して用いることができる。例えば、リン系難燃剤、ブロム化合物や三酸化アンチモン等の難燃剤、及びカーボンブラックや有機染料等の着色剤等を使用することができる。 In the epoxy resin composition of the present invention, in addition to the above components, a mold release agent, a coupling agent, a thermoplastic oligomer, and other components that can be generally used for an epoxy resin composition are appropriately blended and used. be able to. For example, phosphorus-based flame retardants, flame retardants such as bromine compounds and antimony trioxide, and colorants such as carbon black and organic dyes can be used.
離型剤としては、ワックスが使用できる。ワックスとしては、例えばステアリン酸、モンタン酸、モンタン酸エステル、リン酸エステル等が使用可能である。 Wax can be used as the release agent. As the wax, for example, stearic acid, montanic acid, montanic acid ester, phosphoric acid ester and the like can be used.
カップリング剤としては、例えばエポキシシランが使用可能である。カップリング剤の添加量は、エポキシ樹脂組成物に対して、０．１〜２．０ｗｔ％が好ましい。０．１ｗｔ％未満では樹脂と基材のなじみが悪く成形性が悪くなり、逆に２．０ｗｔ％を超えると連続成形性での成形品汚れが生じる。カップリング剤は無機充填材と樹脂成分の接着力を向上させるために用いられる。 As the coupling agent, for example, epoxy silane can be used. The addition amount of the coupling agent is preferably 0.1 to 2.0 wt% with respect to the epoxy resin composition. If it is less than 0.1 wt%, the resin and the base material will not be well-matched, and the moldability will be poor. The coupling agent is used to improve the adhesion between the inorganic filler and the resin component.
熱可塑性のオリゴマー類としては、Ｃ５系およびＣ９系の石油樹脂、スチレン樹脂、インデン樹脂、インデン・スチレン共重合樹脂、インデン・スチレン・フェノール共重合樹脂、インデン・クマロン共重合樹脂、インデン・ベンゾチオフェン共重合樹脂等が例示さえる。添加量としては、通常、エポキシ樹脂１００重量部に対して、２〜３０重量部の範囲である。熱可塑性のオリゴマー類は、エポキシ樹脂組成物の成形時の流動性改良およびリードフレーム等の基材との密着性向上のために用いられる。 Thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, indene / styrene copolymer resins, indene / styrene / phenol copolymer resins, indene / coumarone copolymer resins, indene / benzothiophene. Examples thereof include copolymer resins. As addition amount, it is the range of 2-30 weight part normally with respect to 100 weight part of epoxy resins. Thermoplastic oligomers are used to improve fluidity during molding of the epoxy resin composition and to improve adhesion to a substrate such as a lead frame.
本発明のエポキシ樹脂組成物は、エポキシ樹脂と硬化剤を必須成分として含み、無機充填材等の成分を含む配合成分（カップリング剤を除く）をミキサー等によって均一に混合した後、カップリング剤を添加し、加熱ロール、ニーダー等によって混練して製造することができる。これらの成分の配合順序にはカップリング剤を除き特に制限はない。更に、混練後に溶融混練物の粉砕を行い、パウダー化することやタブレット化することも可能である。 The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent as essential components, and a blending component (excluding a coupling agent) containing components such as an inorganic filler is uniformly mixed by a mixer or the like, and then a coupling agent. And knead | mixing with a heating roll, a kneader, etc. can manufacture. There is no restriction | limiting in particular in the mixing | blending order of these components except a coupling agent. Further, after kneading, the melt-kneaded material can be pulverized to be powdered or tableted.
本発明のエポキシ樹脂組成物は、特に電子部品封止用および放熱基板用として優れるので、電子材料用のエポキシ樹脂組成物として適する。 The epoxy resin composition of the present invention is particularly suitable as an epoxy resin composition for electronic materials because it is excellent for electronic component sealing and heat dissipation substrates.
本発明のエポキシ樹脂組成物は、ガラス繊維等の繊維状基材と複合させて複合材とすることができる。例えば、エポキシ樹脂および硬化剤を主成分としたエポキシ樹脂組成物を有機溶剤に溶解させたものを、シート状繊維基材に含浸し加熱乾燥して、エポキシ樹脂を部分反応させて、プリプレグとすることができる。 The epoxy resin composition of the present invention can be combined with a fibrous base material such as glass fiber to form a composite material. For example, a sheet fiber base material impregnated with an epoxy resin composition mainly composed of an epoxy resin and a curing agent in an organic solvent is impregnated and dried by heating to partially react the epoxy resin to obtain a prepreg. be able to.
本発明のエポキシ樹脂組成物を用いて硬化成形物を得るためには、例えば、トランスファー成形、プレス成形、注型成形、射出成形、押出成形等の加熱成形方法が適用されるが、量産性の観点からは、トランスファー成形が好ましい。 In order to obtain a cured molded product using the epoxy resin composition of the present invention, for example, a heat molding method such as transfer molding, press molding, cast molding, injection molding, extrusion molding or the like is applied. From the viewpoint, transfer molding is preferable.
本発明のエポキシ樹脂組成物は、エポキシ樹脂および硬化剤がともに二官能性のもののみから構成された場合においても、加熱反応させた場合、エポキシ樹脂と硬化剤が反応して生成する水酸基の一部がさらにエポキシ樹脂中のエポキシ基と反応するため、通常は三次元硬化物を与えるが、場合により有機溶剤の使用、硬化促進剤種の選択、および反応温度等の加熱反応条件の制御により、実質的に二次元高分子のみで構成された熱可塑性の成形物とすることができる。 Even when the epoxy resin composition of the present invention is composed only of a bifunctional epoxy resin and a curing agent, when the epoxy resin and the curing agent are heated and reacted, the epoxy resin and the curing agent react with each other. Since this part further reacts with the epoxy group in the epoxy resin, it usually gives a three-dimensional cured product, but in some cases, by use of an organic solvent, selection of a curing accelerator type, and control of heating reaction conditions such as reaction temperature, It can be set as the thermoplastic molding substantially comprised only by the two-dimensional polymer.
本発明の硬化成形物は、高耐熱性、低熱膨張性および高熱伝導性の観点から結晶性を有するものであることが好ましい。成形物の結晶性の発現は、走査示差熱分析で結晶の融解に伴う吸熱ピークを融点として観測することにより確認することができる。好ましい融点は１２０℃から２８０℃の範囲であり、より好ましくは１５０℃から２５０℃の範囲である。また、硬化成形物の好ましい熱伝導率は４Ｗ／ｍ・Ｋ以上であり、特に好ましく６Ｗ／ｍ・Ｋ以上である。 The cured molded product of the present invention preferably has crystallinity from the viewpoints of high heat resistance, low thermal expansion and high thermal conductivity. The expression of the crystallinity of the molded product can be confirmed by observing an endothermic peak accompanying melting of the crystal as a melting point by scanning differential thermal analysis. A preferred melting point is in the range of 120 ° C. to 280 ° C., more preferably in the range of 150 ° C. to 250 ° C. Moreover, the preferable thermal conductivity of the cured molded product is 4 W / m · K or more, and particularly preferably 6 W / m · K or more.
ここで結晶性発現の効果を簡単に説明する。一般的に、エポキシ樹脂硬化物においては耐熱性の指標としてガラス転移点が用いられる。これは、通常のエポキシ樹脂硬化物が結晶性を持たないアモルファス状（ガラス状）の成形物でありガラス転移点を境として物性が大きく変化するためである。従って、エポキシ樹脂硬化物の耐熱性を高くするため、すなわちガラス転移点を高くするためには架橋密度を高くする必要があるが、逆に可撓性が低下し脆くなる欠点があった。これに対して、本発明の硬化成形物は、結晶性を発達させる点に特徴があるが、融点まで物性変化が少ないことから融点を耐熱性の指標とすることができる。高分子物質は、融点の方がガラス転移点よりも高い温度にあるため、本発明の硬化成形物は、低い架橋密度により高い可撓性を維持しつつ、高い耐熱性を確保できる。また、結晶性発現は、高い分子間力を意味しており、これにより分子の運動が抑制され、低熱膨張性の達成とともに、高い熱拡散率が発揮され熱伝導率が向上する。 Here, the effect of crystallinity will be briefly described. Generally, in a cured epoxy resin, a glass transition point is used as an index of heat resistance. This is because a normal epoxy resin cured product is an amorphous (glassy) molded product having no crystallinity, and the physical properties greatly change at the glass transition point. Therefore, in order to increase the heat resistance of the cured epoxy resin, that is, to increase the glass transition point, it is necessary to increase the crosslink density. On the other hand, the cured molded product of the present invention is characterized in that crystallinity is developed, but since the change in physical properties is small up to the melting point, the melting point can be used as an index of heat resistance. Since the polymer material has a melting point higher than the glass transition point, the cured molded product of the present invention can ensure high heat resistance while maintaining high flexibility due to low crosslink density. In addition, the expression of crystallinity means a high intermolecular force, which suppresses the movement of molecules, achieves low thermal expansibility, exhibits high thermal diffusivity, and improves thermal conductivity.
従って、本発明の硬化成形物の結晶化度は高いものほどよい。ここで結晶化の程度は走査示差熱分析での結晶の融解に伴う吸熱量から評価することができる。好ましい吸熱量は、充填材を除いた樹脂成分の単位重量あたり１０Ｊ／ｇ以上である。より好ましくは３０Ｊ／ｇ以上であり、特に好ましくは５０Ｊ／ｇ以上である。これより小さいと成形物としての耐熱性、低熱膨張性および熱伝導率の向上効果が小さい。なお、ここでいう吸熱量は、示差走査熱分析計により、約１０ｍｇを精秤した試料を用いて、窒素気流下、昇温速度１０℃／分の条件で測定して得られる吸熱量を指す。また、結晶化した本発明の硬化成形物は、広角Ｘ線回折においても、明確なピークとして観察することができる。この場合、結晶化度は、全体のピーク面積から結晶化していないアモルファス状樹脂のピークを差引いた面積を全体のピーク面積で除することにより求めることができる。このようにして求めた望ましい結晶化度は１５％以上、より望ましくは３０％以上、特に望ましくは５０％以上である。 Accordingly, the higher the degree of crystallinity of the cured molded product of the present invention, the better. Here, the degree of crystallization can be evaluated from the endothermic amount accompanying the melting of the crystal in the scanning differential thermal analysis. A preferable endothermic amount is 10 J / g or more per unit weight of the resin component excluding the filler. More preferably, it is 30 J / g or more, Most preferably, it is 50 J / g or more. When smaller than this, the improvement effect of the heat resistance, low thermal expansibility, and thermal conductivity as a molded product is small. The endothermic amount referred to here refers to the endothermic amount obtained by measuring with a differential scanning calorimeter using a sample accurately weighed about 10 mg in a nitrogen stream under a temperature rising rate of 10 ° C./min. . Further, the crystallized cured molded product of the present invention can be observed as a clear peak even in wide-angle X-ray diffraction. In this case, the crystallinity can be obtained by dividing the area obtained by subtracting the peak of the amorphous resin that is not crystallized from the entire peak area by the entire peak area. The desired crystallinity thus obtained is 15% or more, more preferably 30% or more, and particularly preferably 50% or more.
本発明の硬化成形物は、上記成形方法により加熱反応させることにより得ることができるが、通常、成形温度としては８０℃から３００℃であるが、成形物の結晶化度を上げるためには、成形物の融点よりも低い温度で反応させることが望ましい。好ましい成形温度は１００℃から２５０℃の範囲であり、より好ましくは１３０℃から２００℃である。また、好ましい成形時間は３０秒から１時間であり、より好ましくは１分から３０分である。さらに成形後、ポストキュアにより、さらに結晶化度を上げることができる。通常、ポストキュア温度は１３０℃から２８０℃であり、時間は１時間から２０時間の範囲であるが、示差熱分析における吸熱ピーク温度よりも５℃から４０℃低い温度で、１時間から２４時間かけてポストキュアを行うことが望ましい。 The cured molded product of the present invention can be obtained by heating reaction with the above molding method. Usually, the molding temperature is 80 ° C. to 300 ° C. In order to increase the crystallinity of the molded product, It is desirable to react at a temperature lower than the melting point of the molded product. A preferred molding temperature is in the range of 100 ° C. to 250 ° C., more preferably 130 ° C. to 200 ° C. The preferable molding time is 30 seconds to 1 hour, more preferably 1 minute to 30 minutes. Further, after molding, the crystallinity can be further increased by post-cure. Usually, the post-cure temperature is 130 ° C. to 280 ° C., and the time is in the range of 1 hour to 20 hours, but the temperature is 5 ° C. to 40 ° C. lower than the endothermic peak temperature in the differential thermal analysis, and it is 1 hour to 24 hours. It is desirable to perform post-cure.
以下実施例により本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
参考例１
４，４’−ジヒドロキシビフェニル１００．０ｇ、４，４’−ジヒドロキシジフェニルメタン５０．０ｇをエピクロルヒドリン７２０ｇ、ジエチレングリコールジメチルエーテル１００ｇに溶解し、６０℃にて、減圧下（約１３０Ｔｏｒｒ）、４８％水酸化ナトリウム水溶液１２７ｇを３時間かけて滴下した。この間、生成する水はエピクロルヒドリンとの共沸により系外に除き、留出したエピクロルヒドリンは系内に戻した。滴下終了後、さらに１時間反応を継続して脱水後、エピクロルヒドリンを留去し、メチルイソブチルケトン９５０ｇを加えた後、水洗を行い、塩を除いた。その後、８５℃にて４８％水酸化ナトリウムを２．８ｇ添加して１時間攪拌し、温水１０００ｍＬで水洗した。その後、分液により水を除去後、メチルイソブチルケトンを減圧留去し、白色結晶状のエポキシ樹脂２１５ｇを得た。
Reference example 1
480.0% aqueous sodium hydroxide solution is prepared by dissolving 100.0 g of 4,4′-dihydroxybiphenyl and 50.0 g of 4,4′-dihydroxydiphenylmethane in 720 g of epichlorohydrin and 100 g of diethylene glycol dimethyl ether at 60 ° C. under reduced pressure (about 130 Torr). 127 g was added dropwise over 3 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour, followed by dehydration. Then, epichlorohydrin was distilled off, and 950 g of methyl isobutyl ketone was added, followed by washing with water to remove the salt. Thereafter, 2.8 g of 48% sodium hydroxide was added at 85 ° C., stirred for 1 hour, and washed with 1000 mL of warm water. Then, after removing water by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 215 g of white crystalline epoxy resin.
このエポキシ樹脂のエポキシ当量は１６８であり、加水分解性塩素は３４０ｐｐｍ、キャピラリー法による融点は１４５℃から１５０℃であり、１５０℃での粘度は６ｍＰａ・ｓであった。ＧＰＣ測定より求められた４，４’−ジヒドロキシビフェニルより得られるエポキシ樹脂のビフェニレン基を１つ含むものが５４％、２つ含むものが５％であった。また、４，４’−ジヒドロキシジフェニルメタンより得られるエポキシ樹脂のジフェニルメタン基を１つ含むものが２４％、２つ含むものが６％であった。ここで、加水分解性塩素とは、試料０．５ｇをジオキサン３０ｍｌに溶解後、１Ｎ−ＫＯＨ、１０ｍｌを加え３０分間煮沸還流した後、室温まで冷却し、さらに８０％アセトン水１００ｍｌを加えたものを、０．００２Ｎ−ＡｇＮＯ3水溶液で電位差滴定を行うことにより測定された値である。また融点とは、キャピラリー法により昇温速度２℃／分で得られる値である。粘度はＢＲＯＯＫＦＩＥＬＤ製、ＣＡＰ２０００Ｈで測定した。また、ＧＰＣ測定は、装置；日本ウォーターズ（株）製、５１５Ａ型、カラム；ＴＳＫ−ＧＥＬ２０００×３本およびＴＳＫ−ＧＥＬ４０００×１本（いずれも東ソー（株）製）、溶媒；テトラヒドロフラン、流量；１ ｍｌ／ｍｉｎ、温度；３８℃、検出器；ＲＩの条件に従った。 The epoxy equivalent of this epoxy resin was 168, hydrolyzable chlorine was 340 ppm, the melting point by capillary method was 145 ° C. to 150 ° C., and the viscosity at 150 ° C. was 6 mPa · s. Of the epoxy resin obtained from 4,4′-dihydroxybiphenyl obtained by GPC measurement, 54% contained one biphenylene group and 5% contained two. Moreover, the thing containing one diphenylmethane group of the epoxy resin obtained from 4,4'-dihydroxydiphenylmethane was 24%, and the thing containing 2 was 6%. Here, hydrolyzable chlorine is obtained by dissolving 0.5 g of a sample in 30 ml of dioxane, adding 1 N-KOH, 10 ml, boiling and refluxing for 30 minutes, cooling to room temperature, and further adding 100 ml of 80% acetone water. Is a value measured by performing potentiometric titration with a 0.002N-AgNO 3 aqueous solution. The melting point is a value obtained by a capillary method at a heating rate of 2 ° C./min. The viscosity was measured with CAP2000H manufactured by BROOKFIELD. In addition, GPC measurement was carried out using a device: Nippon Waters Co., Ltd., Model 515A, column: TSK-GEL2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corp.), solvent: tetrahydrofuran, flow rate: 1 ml / min, temperature; 38 ° C., detector; RI conditions were followed.
このエポキシ樹脂のエポキシ当量は１７９であり、加水分解性塩素は２７０ｐｐｍ、キャピラリー法による融点は１２８℃から１３１℃であり、１５０℃での粘度は１１．６ｍＰａ・ｓであった。得られた樹脂のＧＰＣ測定より求められた一般式（１）における各成分比は、ｎ＝０が９１．０％、ｎ＝１が８．２％であった。 The epoxy equivalent of this epoxy resin was 179, hydrolyzable chlorine was 270 ppm, the melting point by capillary method was 128 ° C. to 131 ° C., and the viscosity at 150 ° C. was 11.6 mPa · s. As for each component ratio in General formula (1) calculated | required from GPC measurement of the obtained resin, n = 0 was 91.0% and n = 1 was 8.2%.
実施例１〜７、比較例１〜４
エポキシ樹脂として、ビフェニル系エポキシ樹脂（エポキシ樹脂Ａ：ジャパンエポキシレジン製、ＹＬ−６１２１（４，４’−ジヒドロキシビフェニルのエポキシ化物と３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシビフェニルのエポキシ化物との１：１の混合物）、エポキシ当量１８３）、参考例１で得たエポキシ樹脂（エポキシ樹脂Ｂ）およびｏ−クレゾ−ルノボラック型エポキシ樹脂（エポキシ樹脂Ｃ：日本化薬製、ＥＯＣＮ−１０２０−６５；エポキシ当量２００）を使用する。硬化剤として、ジェットミルにて粉砕後、分級して得られた平均粒径２．１μｍ（最大粒径７μｍ）の４，４’−ジヒドロキシビフェニル（硬化剤Ａ）、ジェットミルにて粉砕した平均粒径５．６μｍ（最大粒径１１．３μｍ）の４，４’−ジヒドロキシビフェニル（硬化剤Ｂ）、フェザーミルにて粉砕した平均粒径１２．８μｍ（最大粒径２８．４μｍ）の４，４’−ジヒドロキシビフェニル（硬化剤Ｃ）、平均粒径５４μｍ（最大粒径１２０μｍ）の４，４’−ジヒドロキシビフェニル（硬化剤Ｄ）、４，４’−ジヒドロキシジフェニルメタン（硬化剤Ｅ）、フェノ−ルノボラック（硬化剤Ｆ：群栄化学製、ＰＳＭ−４２６１；ＯＨ当量１０３、軟化点 ８０℃）を使用する。硬化促進剤としてトリフェニルホスフィン、無機充填材として、球状アルミナ（平均粒径１２．２μｍ）を使用する。硬化剤の粒径において最大粒径とは、全量の９９ｗｔ％が通過する最小径であり、平均粒径はメデアン径である。
Examples 1-7, Comparative Examples 1-4
As an epoxy resin, biphenyl type epoxy resin (epoxy resin A: manufactured by Japan Epoxy Resin, YL-6121 (epoxidized product of 4,4′-dihydroxybiphenyl and 3,3 ′, 5,5′-tetramethyl-4,4 ′ -1: 1 mixture with epoxidized product of dihydroxybiphenyl), epoxy equivalent 183), epoxy resin (epoxy resin B) obtained in Reference Example 1 and o-cresol-novolak type epoxy resin (epoxy resin C: Nippon Kayaku) Manufactured, EOCN-1020-65; epoxy equivalent 200). As a curing agent, 4,4′-dihydroxybiphenyl (curing agent A) having an average particle diameter of 2.1 μm (maximum particle diameter 7 μm) obtained by pulverization with a jet mill and classification, an average pulverized with a jet mill 4,4′-dihydroxybiphenyl (curing agent B) with a particle size of 5.6 μm (maximum particle size 11.3 μm), 4,4 with an average particle size of 12.8 μm (maximum particle size 28.4 μm) pulverized by a feather mill 4′-dihydroxybiphenyl (curing agent C), 4,4′-dihydroxybiphenyl (curing agent D) having an average particle size of 54 μm (maximum particle size 120 μm), 4,4′-dihydroxydiphenylmethane (curing agent E), pheno- Lunovolak (curing agent F: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent 103, softening point 80 ° C.) is used. Triphenylphosphine is used as a curing accelerator, and spherical alumina (average particle size 12.2 μm) is used as an inorganic filler. The maximum particle size in the particle size of the curing agent is the minimum diameter through which 99 wt% of the total amount passes, and the average particle size is the median diameter.
表１に示す成分を配合し、ミキサーで十分混合した後、加熱ロールで約５分間混練したものを冷却し、粉砕してそれぞれ実施例１〜７、比較例１〜４のエポキシ樹脂組成物を得た。このエポキシ樹脂組成物を用いて１７０℃、５分の条件で成形後、１７０℃で１２時間ポストキュアを行い成形物を得て硬化成形物を得て、その物性を評価した。結果をまとめて表１に示す。なお、表１中の各成分の数字は重量部を表す。 After blending the components shown in Table 1 and mixing thoroughly with a mixer, the mixture kneaded for about 5 minutes with a heating roll was cooled and ground to obtain the epoxy resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4, respectively. Obtained. Using this epoxy resin composition, after molding at 170 ° C. for 5 minutes, post-curing was carried out at 170 ° C. for 12 hours to obtain a molded product to obtain a cured molded product, and its physical properties were evaluated. The results are summarized in Table 1. In addition, the number of each component in Table 1 represents parts by weight.
［評価］
（１）熱伝導率
熱伝導率は、ＮＥＴＺＳＣＨ製ＬＦＡ４４７型熱伝導率計を用いて非定常熱線法により測定した。
（２）融点、融解熱の測定（ＤＳＣ法）
示差走査熱量分析装置（セイコーインスツル製ＤＳＣ６２００型）を用い、昇温速度１０℃／分で測定した。
（３）線膨張係数、ガラス転移温度
線膨張係数およびガラス転移温度は、セイコーインスツル（株）製ＴＭＡ１２０Ｃ型熱機械測定装置を用いて、昇温速度１０℃／分にて測定した。
（３）吸水率
直径５０ｍｍ、厚さ３ｍｍの円盤を成形し、ポストキュア後、８５℃、相対湿度８５％の条件で１００時間吸湿させた後の重量変化率とした。
（４）保存安定性
保存安定性はエポキシ樹脂組成物を２５℃、１週間放置後のスパイラルフロー残存率で表した。
[Evaluation]
(1) Thermal conductivity Thermal conductivity was measured by the unsteady hot wire method using an LFA447 type thermal conductivity meter manufactured by NETZSCH.
(2) Measurement of melting point and heat of fusion (DSC method)
Using a differential scanning calorimeter (Seiko Instruments DSC6200 type), the temperature was increased at a rate of 10 ° C./min.
(3) Linear expansion coefficient and glass transition temperature The linear expansion coefficient and glass transition temperature were measured at a temperature elevation rate of 10 ° C / min using a TMA120C type thermomechanical measuring device manufactured by Seiko Instruments Inc.
(3) Water absorption rate A disk having a diameter of 50 mm and a thickness of 3 mm was formed, and after post-curing, the weight change rate after absorbing for 100 hours under the conditions of 85 ° C. and relative humidity of 85% was used.
(4) Storage stability The storage stability was represented by the residual rate of spiral flow after leaving the epoxy resin composition at 25 ° C. for 1 week.
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| EP2371980A1 (en) | 2010-03-25 | 2011-10-05 | Daido Tokushuko Kabushiki Kaisha | Heat resistant steel for exhaust valve |
| JP2011225645A (en) * | 2010-04-15 | 2011-11-10 | Tokyo Univ Of Science | Fine particle for curing epoxy resin, and method for producing the same |
| JP2012120774A (en) * | 2010-12-10 | 2012-06-28 | Fujifilm Corp | Illumination optical system unit for endoscope and method of manufacturing the same |
| WO2013015659A2 (en) * | 2011-07-28 | 2013-01-31 | Lg Innotek Co., Ltd. | Epoxy resin compound and radiant heat circuit board using the same |
| JP2013183527A (en) * | 2012-03-01 | 2013-09-12 | Sumitomo Bakelite Co Ltd | Fixing resin composition, rotor and automobile |
| JP2014122337A (en) * | 2012-11-22 | 2014-07-03 | Asahi Kasei E-Materials Corp | Novel liquid crystalline epoxy resin and composition thereof |
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| JP2020063433A (en) * | 2018-10-17 | 2020-04-23 | 東洋紡株式会社 | Thermally conductive resin composition |
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| EP2371980A1 (en) | 2010-03-25 | 2011-10-05 | Daido Tokushuko Kabushiki Kaisha | Heat resistant steel for exhaust valve |
| JP2011225645A (en) * | 2010-04-15 | 2011-11-10 | Tokyo Univ Of Science | Fine particle for curing epoxy resin, and method for producing the same |
| JP2012120774A (en) * | 2010-12-10 | 2012-06-28 | Fujifilm Corp | Illumination optical system unit for endoscope and method of manufacturing the same |
| EP2731993B1 (en) * | 2011-07-12 | 2023-08-30 | LG Innotek Co., Ltd. | Epoxy resin compound and radiant heat circuit board using the same |
| WO2013015659A2 (en) * | 2011-07-28 | 2013-01-31 | Lg Innotek Co., Ltd. | Epoxy resin compound and radiant heat circuit board using the same |
| WO2013015659A3 (en) * | 2011-07-28 | 2013-05-02 | Lg Innotek Co., Ltd. | Epoxy resin compound and radiant heat circuit board using the same |
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| CN103842434A (en) * | 2011-07-28 | 2014-06-04 | Lg伊诺特有限公司 | Epoxy resin compound and radiant heat circuit board using the same |
| US9357630B2 (en) | 2011-07-28 | 2016-05-31 | Lg Innotek Co., Ltd. | Epoxy resin compound and radiant heat circuit board using the same |
| JP2013183527A (en) * | 2012-03-01 | 2013-09-12 | Sumitomo Bakelite Co Ltd | Fixing resin composition, rotor and automobile |
| JP2015519459A (en) * | 2012-06-14 | 2015-07-09 | ヘクセル コンポジッツ、リミテッド | Improvement of composite materials |
| JP2014122337A (en) * | 2012-11-22 | 2014-07-03 | Asahi Kasei E-Materials Corp | Novel liquid crystalline epoxy resin and composition thereof |
| WO2017145409A1 (en) * | 2016-02-25 | 2017-08-31 | 日立化成株式会社 | Epoxy resin molding material, molded product, molded cured product, and method for producing molded product |
| US20210292545A1 (en) * | 2018-08-22 | 2021-09-23 | Toray Industries, Inc. | Prepreg |
| JP2020063433A (en) * | 2018-10-17 | 2020-04-23 | 東洋紡株式会社 | Thermally conductive resin composition |
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